1. Field of the Invention
The present invention generally concerns fluoropolymeric compositions. In particular, the invention concerns an improved composition that is isolated from an aqueous blend of fluoroelastomer and microparticulate fluoroplastic materials. The improved composition is particularly useful as a manageable intermediate in the development of microfiber-reinforced fluoropolymeric components.
2. Description of the Prior Art
Polytetrafluoroethylene (PTFE) is in many respects an unusual polymer. It is exceptional in its chemical inertness as a result of the strength of its carbon-fluorine bonds and shielding of its carbon-carbon bonds by the bulky fluorine atom. PTFE is exceptionally useful for high temperature applications because it has a high melting point and remains chemically inert at high temperatures. In addition, PTFE""s unusually low frictional coefficient, surface free energy, and dielectric constant all testify to its unusual morphological structure. While these extremely attractive properties cause PTFE to be useful in a broad array of end use applications, they also lead to an unusual set of problems in characterizing some properties of PTFE as well as to difficulties in processing compositions based on PTFE.
The inertness and insolubility of PTFE make it virtually impossible to characterize the molecular weight of a PTFE component by direct, conventional means such as osmometry. The prior art typically resorts to indirect means, such as the determination of specific gravity after recrystallization from a melt at a controlled rate of cooling, as an indicator of molecular weight. The higher the molecular weight of the PTFE, the longer its chain length and the more difficult it is to recrystallize to a highly ordered (crystalline) and, therefore, dense structure. Consequently, the specific gravity of PTFE at any given crystallinity level is an indirect measure of molecular weight. Crystallinity may be independently assessed by X-ray crystallography or calorimetry, and the specific gravity obtained upon cooling (recrystallizing) a PTFE melt at a prescribed rate (referred to as the standard specific gravity (SSG)) is a commonly employed measure of molecular weight.
It is well established that certain physical behavior of PTFE is a strong function of molecular weight and crystallinity (Blair, John A., Fluorocarbons, Polymers, xe2x80x9cEncyclopedia of Industrial Chemical Analysis,xe2x80x9d vol. 13, pps. 73-93). For example, most commercial molding powders of PTFE have a very high molecular weight corresponding to an SSG of between about 2.16 and 2.25, depending on crystallinity. High molecular weight is needed to develop adequate tensile strength and the elongation required for typical end uses of an essentially waxy polymer.
At lower molecular weight, PTFE becomes very weak and brittle while retaining its low coefficient of friction. Low molecular weight PTFE is typically a friable powder, which can be very highly crystalline, and enjoys use as a dry lubricant.
An important distinction in behavior between low molecular weight and high molecular weight PTFE lies in the propensity of the high molecular weight PTFE to fibrillate when in its highly crystalline, as-polymerized condition upon being subjected to mechanical shear stresses. Low molecular weight PTFE, on the other hand, simply reaches its ultimate elongation at low stress and disintegrates into a lubricating (low coefficient of friction) powder while highly crystalline high molecular weight PTFE substantially transforms its morphological character under shear and forms an extensive network of fibers. This is most obvious in the case of aqueous, dispersion-polymerized, high molecular weight PTFE in which the growing polymer chains are highly organized into dense, tightly packed spheres or rods with a very high degree of crystallinity. The rod-shaped particles, when present, typically have a length to diameter ratio (L/D) of 2-3:1 and the diameter is typically on the order of 0.1 micron (xcexc). The spherical particles typically have a diameter of approximately 0.2-0.3xcexc, as measured by light scattering. Because of their very high crystallinity and high molecular weight, it is possible for these particles to fibrillate into rod-like structures when subjected to a relatively low mechanical shear force, forming fibers having a very high L/D ratio. These PTFE fibers have the ability to form aggregated structures in which the rod-like aggregates of high molecular weight PTFE serve as a microfiber reinforcement within the polymer mass of fibrillated and unfibrillated PTFE. The presence of such structures results in an increase in the tensile modulus and strength of the polymer matrix in which they are present and for this reason may be referred to as a microfiber reinforcement. The ease with which such fiber formation occurs is such that one must take great care to control the level and direction of applied shear forces to avoid uncontrolled entanglement of propagating fibers which can result in physical unmanageability during subsequent processing.
Melt viscosity is another commonly measured surrogate for molecular weight of polymers such as PTFE. Commonly measured at 380xc2x0 C., the melt viscosity of high molecular weight PTFE is typically about 1010 to 1012 poise. High molecular weight PTFE readily forms fibers of the type discussed above when at a high level of crystallinity. As the melt viscosity at 380xc2x0 C. decreases (indicating lower molecular weight), however, PTFE""s ability to fibrillate falls off markedly. Below about 109 poise, PTFE becomes a much more brittle, friable material.
Many attempts have been made in the prior art to combine PTFE with other polymeric compounds, such as elastomers, to form multicomponent systems. Fairly sophisticated processes have been developed to control the properties of such multicomponent systems, and skilled artisans have been able to enhance various desirable properties of final products created from such multicomponent systems. xe2x80x9cRubber-toughenedxe2x80x9d plastics are a good example of such an enhancement.
In creating these multicomponent systems, skilled artisans have used with some success xe2x80x9cmicroparticulate polymersxe2x80x9d, i.e., emulsions and dispersions of elastomeric and plastic polymers, as coating and casting fluids. Various processes have been developed for applying such fluids, blended in the microparticulate state, enabling skilled artisans to thermally consolidate thin films in an extremely short duration of time and at surprisingly high temperatures, if necessary. Short interval thermal processing yields surprisingly compatible blends of microparticulates, even those with greatly disparate melt flows. For example, these processes have been used to combine polymers perceived to be non-extrudable due to their high viscosity or molecular weights or to combine non-melt-processible polymers, such as PTFE, with other more flowable polymeric components. Short interval thermal processing has also been used to combine materials with vastly different melting points (ranging from 150xc2x0 C. to 335xc2x0 C.). The absence of substantial mechanical shear during the high temperature phase of the thermal consolidation avoids mechanically-induced thermal deterioration of molecular weight in the materials, such as might occur during a melt-extrusion process.
Despite all of these efforts, the prior art has not been able to develop blended solid compositions containing fluoroplastics at particularly high useful levels into fluoroplastic/fluoroelastomer blends, while maintaining facile processibility of the blends.
Polymeric intermediates (for example, gum rubbers) must first be isolated before they can be compounded into a processible composition that can incorporate fillers, such as carbon or talc. The initial isolation of the polymeric intermediate generally involves the steps of coagulating the polymer from a polymerization medium, followed by washing the polymer, drying the polymer, and compacting the polymer into a slab. This polymeric slab is then mixed with desired curing additives and fillers on a high shear mill, such as a Banbury mill, keeping the mixture below temperatures that would initiate localized or premature cure of the rubber compound. Such premature cure is known in the art as xe2x80x9cscorch.xe2x80x9d Other additives may be incorporated in a similar manner. Fillers are generally incorporated before the curatives because the incorporation process generates heat, which would cause scorch if the curative were present. The amount of such additives is limited because additional space in the compound is needed to accommodate the presence of the curative. Additives and curatives are added sequentially, which overall affects the workability of the gum. Once the additives and curatives are added, the compound is stored at a cool temperature until used. The compounded formulation is then typically xe2x80x9cfreshenedxe2x80x9d on a mill or calender and extruded at non-scorching conditions to yield a form that may be compression-molded, transfer-molded, or injection-molded to produce a shaped, cured part such as an xe2x80x9coxe2x80x9d-ring or seal. Cured parts may then be demolded and post-cured at elevated temperatures to develop maximal mechanical properties or chemical resistance.
The prior art evidences substantial effort to identify desirable fillers and curing additives that improve end properties. PTFE has been identified as an excellent filler because of its desirable tribological properties. The prior art processes incorporating milled PTFE, however, have been limited to filler loadings below 25 parts per hundred rubber by weight to avoid problems both during milling and in subsequent processing. Furthermore, the prior art has also been constrained to employ low molecular weight PTFE micropowder, such as DuPont""s MP 1000, as a filler. For this reason, users of such blends have not been able to exploit the benefits of high molecular weight PTFE related to its tendency to fibrillate under applied mechanical shear. Thus, the prior art processes have not generally been able to achieve a processible composition as a blended solid containing a high filler loading of PTFE, and particularly with high molecular weight PTFE. The potential benefits of a homogeneously distributed, high molecular weight PTFE at a high filler loading in the compositions have been, consequently, forgone.
The present invention achieves the desirable benefits discussed above through the use of an essentially non-fibrillating, low-shear isolation process that incorporates in excess of 25%, and typically 40-50%, and as high as 80% by weight of a plastic (particularly high molecular weight PTFE, a perfluoroplastic) into the rubber (based on total polymer weight). The process yields compositions containing the plastic PTFE in an unfibrillated form, yet the PTFE is fibrillatable and may be fibrillated by subsequent processing. The range of the substantial benefits obtained are described as follows.
It is a prime objective of the invention to produce a curable, solid composition containing (i) an elastomer, preferably a fluoroelastomer, and (ii) a fluoroplastic at greater than 25% by weight based on total polymer, wherein the fluoroplastic is in an unfibrillated yet fibrillatable state. Fluoroplastics useful in the invention include: perfluoroplastic(s), such as PTFE or copolymers of tetrafluoroethylene (TFE) with hexafluoropropylene (HFP); perfluorovinyl ethers; or, other halogenated ethylenic monomers, such as vinylidene fluoride (VF2), chlorotrifluoroethylene (CTFE), or vinyl fluoride (VF). Ethylene and propylene copolymers of TFE and HFP are also envisioned as applicable plastics in this invention. The particulate fluoroplastic and elastomers have a particle size in the range of 0.00 1xcexc to 1.0xcexc, i.e., xe2x80x9cmicron-sized,xe2x80x9d thus their designation or definition as xe2x80x9cmicroparticulate.xe2x80x9d
A further objective of this invention is to obtain curable compositions isolated directly from aqueous blends of the elastomer and plastic microparticulates. Such isolation may be as a thin film or as a powder that may be extruded well below the melting point or softening point of the plastic component and above the glass transition temperature of the elastomeric component. The curable composition may also take the form of a gel. The solid forms, which can contain curatives, may be directly molded by, for example, compression molding methods to directly produce cured elasto-plastic parts such as diaphragms or xe2x80x9coxe2x80x9d-rings.
It is yet a further objective of this invention to demonstrate the superior performance properties of cured compounds or parts created from compositions of the invention in regard to mechanical behavior (notably, retention of high elongation, reduced coefficient of friction, reduced wear rate), as well as very good resistance to swell in solvents or fuels. It is also an objective to demonstrate good capability for high temperature end use for such parts.
It is also an objective to show that the useful properties of parts processed from these blends may be tailored through selective choice of process temperatures to achieve selectively crosslinked or melted morphological domains specific to the melting points or cross-linking propensities of the various plastic or elastomeric components.
Lastly, it is an objective to demonstrate that such solids isolated from these aqueous blended polymers may be subsequently subjected to mechanical forces to induce fiber formation by the particulates, particularly of the high molecular weight PTFE component, to obtain microfiber-reinforced composites with unique mechanical behavior.
Importantly, the process described to achieve these excellent or superior properties employs the least costly form of the selected polymers. Polymerized emulsions and dispersions, in principle, represent a preferred lowest cost position for the resin. Particularly for materials-intensive components, such as those based on fluoropolymers, this may be a decisive advantage. The compounds and processes of the invention provide for the use of PTFE as a filler, which can be more cost-effective than conventional fillers because the PTFE can be filled to a higher loading than is normally practiced. The PTFE filler of the invention is a polymer with its own strength potential and elongation potential through fibrillationxe2x80x94as well as temperature and chemical resistance properties that can exceed those of a hydrogen-containing fluoroelastomer.